Selective herbicide compositions containing a substituted triazine derivative and a benzo-2-thia-1,3-diazinone-(4)-2,2-dioxide

ABSTRACT

A herbicide comprising a mixture of a substituted triazine derivative with a benzo-2-thia-1,3-diazinone-(4)-2,2-dioxide derivative, and a process for controlling the growth of unwanted plants with these mixtures.

United States Patent Fischer 51 Nov. 18, 1975 SELECTIVE HERBICIDE COMPOSITIONS [52] US. Cl 71/91; 71/93 CONTAINING A SUBSTITUTED TRIAZINE [51] Int. Cl? A01N 9/12 DERIVATIVE AND A [58] Field of Search 71/91, 93 BENZO-Z-THIA-l,3-DIAZlNONE-(4)-2,2- DIOXIDE [56] References Cited [75] Inventor: Adolf Fischer, Mutterstadt, UNITED STATES PATENTS Germany PIIOIS. et 3.1. 3.62l,017 11/1971 Zeidler et a1. 71/91 [73] Assigneez Badische Anilin- & S0da-Fabrik 3,708,277 1/ 1973 Zeidler et a1. 71/91 Aktiengesellschaft, Ludwigshafen 3,787,198 1/1974 Hagimato et a1. 71/118 (Rhine), Germany Primary Examiner-James 0. Thomas, Jr. [22] Filed" 1973 Attorney, Agent, or FirmJohnston, Keil, Thompson [21] Appl. No.: 334,195 & Shurtleff Relatetl US. Application Data ABSTRACT [63] Contmuatlon-m-part of Ser. No. 16,567, March 4. 1970 abandoned A herb1c1 de eomprlsmg a mixture of a snbstltuted triazrne derlvatwe w1th a benzo-2-th1a-1 ,3-d1az1none-(4)- [30] Foreign Application Priority Data 2,2-dioxide derivative, and a process for controlling Mar. 15, 1969 Germany 1913266 the growth of unwanted plants with these mixtures.

2 Claims, N0 Drawings SELECTIVE IIERBICIDE COMPOSITIONS CONTAINING A SUBSTITUTED TRIAZINE DERIVATIVE AND A BENZO-Z-TIIIA-l,3-DIAZINONE-(4)-2,2-DIOXIDE RELATED APPLICATION where X denotes chlorine, bromine, thiomethyl or methoxyl, R denotes a methyl, ethyl, isopropyl, methoxyisopropyl, ethoxyisopropyl radical, or the group cn ci-l-cu,

or its salts, and R denotes an ethyl, isopropyl, tertbutyl, methoxypropyl, B-methoxyethyl, methoxyisopropyl, ethoxyisopropyl, propoxyisopropyl, thiomethylisopropyl, isopentynyl- I :a, a-(bisethyD-ethyl, a, -a-(bismethyl) propyl, a-

cyanoisopropyl, isobutynylv H;- 3 (CH e B-cyanoethylor cyanopropyl radical, and v 'b. a a' benzo-Zthia-l,3 diazinone-(4)-2-,2derivative having the formula v v where R denotes a methyl, ethyl or isopropyl radical or their salts has a good herbicidal action. By salts we mean the alkali metal (potassium, sodium), alkaline "earth metal (calcium, magnesium), ammonium or amine salts (dimethylamine, diethylamine, ethanolamine, diethanolamine, N,N-dimethylethanolamine).

The ratios of the components of the mixture may be varied at will; however, mixtures of l'part by weight of a triazine derivative (a) to 0.1 to 10 parts by weight, particularly 0.2 to 5 parts by weight, of compound (b), are preferred.

Used selectively, the mixtures are especially effective on weed floras containing millet or sedge species.

The triazine active ingredients may be prepared for example by reacting cyanuric chloride, in the presence of a compound which binds hydrogen halide, with the appropriate alkyl-, alkynylor alkoxyalkylamines and, if X is not chlorine, with an alkali metal methylate, an

alkali metal methylmercaptide, or an alkali metal cyanide in any sequence. Preparation of 2-chloro-4-ethylamine-6-(butyn-l-yl-3- amino)-s-tri-azine:

At a temperature of l0 to 20C, 135 parts by weight of ethylamine is added dropwise to a solution of 276 parts by weight of cyanuric chloride in 900 parts by weight of acetone. The mixture is subsequently stirred for an hour at l0 to 20C and the precipitate formed is filtered off. The filtrate is freed, at room temperature and in vacuo, from solvent and the crystalline residue is recrystallized from cyclohexane. 233 parts by weight of 2,4-dichloro-6-ethylamino-s-triazine having a melting point of 103 to 105C is obtained.

9.65 parts by weight of 2,4-dichloro-6-ethylamine-striazine is dissolved in 50 parts by weight of acetone; at a temperature of 15 to 20C, a solution of 7 parts by weight of butyn-l-yl-3-amine in 25 parts by weight of acetone is then added. The mixture is subsequently stirred for 20 hours at room temperature (20C) and the precipitate formed is then filtered off. The filtrate is freed from solvent in vacuo and the crystalline residue is recrystallized from cyclohexane. 10.5 parts by weight of 2-chloro-4-ethylamino-6-( butyn- 1 -yl-3-amino )-striazine having a melting point of 140C is obtained. Preparation (butynl-yl-3-amino -s-triazine:.

At a temperature of l0 to 20C, a solution of 48 parts by weight of methylmercaptan in 360 parts by weight of water in one dropping funnel and a solution of 40 parts by Weight of sodium hydroxide in 360 parts by weight of water in a second dropping funnel are added simultaneously to a solution of 184 parts by weight of cyanuric chloride in 3,000 parts by weight-of ethyl acetate. The mixture is subsequently stirred for 2 hours at -l0C. The organic phase is then separated and dried with magnesium sulfate, and the solvent is removed in vacuo at a temperature of up to 35C. The

crystalline residue is recrystallized from ligroin.

parts by weight of 2-methylmercapto-4,6-dichlorostriazine having a melting point of 58 to 60C is obtained.

9.8 parts by weight of 2-methylmercapto-4,6- dichloro-s-triazine is suspended in 25 parts by weight of water and 15 parts by weight of acetone; 5.25 parts by weight of butyn-l-yl-3-amine hydrochloride, dissolved in 10 parts by weight of water, is then added. At a temperature of 25 to 40C, a solution of 4 parts by weight of sodium hydroxide in 15 parts by weight of water is then added dropwise to this mixture. The reaction mixture is subsequently stirred for a few hours at 35C, the oil which has separated is extracted with methylene chloride and the methylene chloride solution dried with magnesium sulfate. The solvent is removed in vacuo.

of 2-r nethylmercapto-4-ethylamino-6-- The oily residue becomes solid when triturated with ligroin. 9 parts by weight of Z-methylmercapto-4-chloro- 6-(butyn-l-yl-3-amino)-s-triazine having a melting point of 56 to 58C is obtained. 5.7 parts by weight of 2-methylmercapto-4-chloro-6-(butyn-1-y1-3-amino)-striazine is suspended in 25 parts by weight of water, 10 parts by weight of acetone and 3.5 parts by weight of 35% aqueous ethylamine solution; the mixture is heated under reflux and a solution of 1 part by weight of sodium hydroxide in 5 parts by weight of water is added dropwise. The mixture is then stirred for 3 hours at boiling temperature and cooled to room temperature. The oil which has separated is extracted with methylene chloride, the organic phase is dried and the solvent removed in vacuo. When toluene is added and the whole cooled, the oily residue becomes crystalline. 4.8 parts by weight of 2-methylmercapto-4-ethylamino- 6-(butyn-l-yl-3-amino)-s-triazine having a boiling point of 95 to 97 is obtained.

At a temperature of 10 to C, 90 parts by weight of ethylamine is added dropwise to 189 parts by weight of cyanuric chloride dissolved in 600 parts by weight of acetone. The reaction mixture is subsequently stirred for an hour at 10 to 20C, the precipitated ethylamine hydrochloride is suction filtered and the filtrate freed from solvent in vacuo. The crystalline residue is recrystallized from cyclohexane. 189 parts by weight of 2,4-dichloro-6-ethylamino-l,3,5,- triazine having a melting point of 103 to 105C is obtained.

At a temperature of 20 to 30C, 13.2 parts by weight of a-methyl-B-methoxyethylamine is one dropping funnel and a solution of 6 parts by weight of sodium hydroxide in 20 parts by weight of water in a second dropping funnel are added simultaneously to a solution of 29 parts by weight of 2,4-dichloro-6-ethylamino-1,3,5,- triazine in 200 parts by weight of acetone. Stirring is subsequently carried out for a fairly long period of time at room temperature (20C); the reaction mixture is filtered and the filtrate freed from solvent in vacuo. The crystalline residue is recrystallized from cyclohexane. 24 parts by weight of 2-chloro-4-ethylamino-6-(amethyl-B-methoxyethyl)-amino-1,3,5-triazine having a melting point of 96C is obtained.

At 20to 25C, 70 parts by weight of distilled B- aminopropionitrile is dripped into a solution of 97 parts by weight of 2-ethylamino-4,6-dich1orotriazine-(1,3,5) in 400 parts by weight of acetone. Stirring is continued overnight, the crystalline product is suction filtered, dissolved in acetone, concentrated, and the concentrate washed with water, filtered again and the dry product recrystallized from acetone; m.p. 215 to 216C (yield: 85% of the theory).

Some of the new active ingredients are listed below:

2-chloro-4-isopropylamino-6-( oz-methyl-B-methoxyethyl)-amino-1,3,5-triazine, m.p. 124 to 125C; 2-chloro-4-ethylamino-6-( a-methyl-B-methoxyethyl)-amino-1,3,5-triazine, m.p. 96C; 2-chloro-4-methylamino-6-( a-methyl-B-methoxyethyl)-amino-l,3,5-triazine, m.p. 129 to 130C; 2-thiometh yl-4-ethylami no-6-( ,B-methylthioethyl amino-l,3,5-triazine, m.p. 109 to 110C; 2chloro-4-isopropylamino-6-(B-cyanoethyl)-amino- 1,3,5-triazine, m.p. 191 to 192C; 2-methyl-4- chloro-6-cyanomethylamino-1,3,S-triazine, m.p. 252 to 253C;

2-ethylamino-4-chlor-6-cyanomethylaminol ,3 ,5-

triazine, m.p. 233 to 235C;

4 2-isopropylamino-4-chloro-6-cyanomethylamino- 1,3,5-triazine, m.p. 191 to 192C; 2chloro-4-tert-butylamino-6-cyanomethylamino- 1,3,5-triazine, m.p. 150 to 151C; 2-chloro-4-cyanomethylamino-6-n butylamino- 1,3,5-triazine, m.p. 170 to 171C; 2-chloro-4-ethy1amino-6-(3-methylbutyn-1yl3- amino)-s-triazine, m.p. to 137C; 2-chloro-4-isopropy1amino-6-(3-methylbutyn-1-yl-3- amino)-s-trazine, m.p. 146 to 148C; 2-methylmercapto-4-ethy1amino-6-(butyn- 1 yl-3- amin0)-s-triazine, m.p. 95 to 97C; 2-chloro-4-isopropylamino-6-( butyn- 1 yl-3-amino s-triazine, m.p. 170 C; 2-chloro-4-ethylamino-6-(butyn-1-yl-3-amino)-striazine, m.p. C;

2-chloro-4,6-bis-(butynl y1-3-amino )-s-triazine; m.p.

The agents according to this invention may be used as solutions, emulsions, suspensions or dusts. The form of application depends entirely on the purpose for which the agents are being used; in any case it should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, the solution in water is suitable. However, hydrocarbons having boiling points higher than 150C, e. g., tetrahydronaphthalene or alkylated naphthalenes, or organic liquids having boiling points higher than 150C and one or more than one functional group, e. g., the keto group, ether group, ester group or amide group, this group being attached as substituent to a hydrocarbon chain or being a component of a heterocyclic ring, may also be used as spray liquids.

Aqueous formulations may be prepared from emulsion concentrates, pastes or wettable powders by adding water. To prepare emulsions the ingredients as such or dissolved in a solvent may be homogenized in water or organic solvents by means of wetting or dispersing agents, e. g., polyethylene oxide adducts. Concentrates which are suitable for dilution with water may be prepared from active ingredient, emulsifying or dispersing agent and possibly solvent.

Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier, e. g., diatomaceous earth, talc, clay or fertilizers.

The active ingredients according to the invention may be used in admixture with fertilizers, other herbicides, fungicides and insecticides.

EXAMPLE 1 The plants Indian Corn (Zea mays), annual bluegrass (Poa annua), barnyard grass (Echinochlaa crus-galli), green foxtail (Setaria viridis), smallflower umbrellaplant (Cyperus difformis), purple nutsedge (Cyperus r0- rundus), ladysthumb (Polygonum persicaria), and tall morningglory (Ipomoea purpurea) are treated at a growth height of 5 to 19 cm with he stated amounts of the following active ingredients and mixtures of them, each amount and each mixture being dispersed in 500 liters of water per hectare:

I 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 0.5 and 2 kg per hectare;

3-isopropyl-2,l ,3-benzothiadiazinone-( 4)-2,2- dioxide, 1.5 and 2 kg per hectare;

1+ 11 0.5 1.5 kg per hectare.

After 5 to 7 days in warm weather, it is ascertained that the onset of action of the mixture on the grass weedsis considerably quicker than that of the individ- 5' ual active ingredients; moreover, the compatibility of the mixture with Indian corn is good.

The results of the experiment are given in the following table:

kg per hectare of I II I II active ingredient 0.5 2 1.5 2 0.5 [.5

Zea mays 0 O 0 0- Poa annua 75 I00 80 Echinochloa crus-galli l5 5 5 10 25 0 Setaria viridis IO 45 O 5 l5 Cyperus difformis IO 40 80 90 95 Cyperus rotundus I0 35 60 85 95 Polygonum persicaria 75 65 80 85 Ipomoea purpurea 5 20 30 45 45 O no damage I 100 complete destruction 5 EXAMPLE 2 In the open, the plants Indian corn (Zea mays), red- 20 root pigweed (Amaranthus retroflexus), purple nutsedge (Cyperus rotundus), large crabgrass (Digitaria sanguinalis), common purslane (Portulaca oleracea) and giant foxtail (Setaria faberii) were treated at a growth height of 2 to 17 cm with the following amounts of the following individual active ingredients and mixtures thereof:

I 3-isopropyl-2, l ,3-benzothiadiazinone-(4)-2,2-dioxide, sodium salt 0.25, 0.5, 0.75 and 1.0 kg/ha;

II 3-isopropyl-2, l ,3-benzothiadiazinone-(4)-2,2-

dioxide, dimethylamine salt 0.25, 0.5, 0.75 and 1.0 kg/ha;

6 III 3-isopropyl-2,l ,3-benzothiadiazinone-(4)-2,2- dioxide, diethanolamine salt 0.25, 0.5 0.75 and 1.0 kg/ha; IV 3-isopropyl-2,l ,3-benzothiadiazinone-(4)-2,2-

dioxide, 0.25, 0.5, 0.75 and 1.0 kg/ha; V 2-ethylamino-4-( l-methyl-3-oxabutyl)-amino-6- chlorol ,3 ,5-triazine, 0.25, 0.5, 0.75 and 1.0 kg/ha;

VI 2-chloro-4-ethylamino--isopropylamino-l ,3 ,5-

triazine, I 0.25, 0.5, 0.75 and 1.0 kg/ha;

I+ V 0.25 0.75, 0.75 0.25, 0.5 +0.5 and 0.25

0.25 kg/ha;

II +V 0.25 +0.75, 0.75 +0.25, 0.5 +0.5 and 0.25

0.25 kg/ha;

III V 0.25 0.75, 0.75 0.25, 0.5 0.5 and 0.25

+ 0.25 kg/ha;

IV V 0.25 0.75, 0.75 0.25, 0.5 0.5 and 0.25

+ 0.25 kg/ha;

I VI 0.25 0.75, 0.75 0.25, 0.5 +0.5 and 0.25

0.25 kg/ha;

I II VI 0.25 0.75, 0.75 0.25, 0.5 0.5 and 0.25

+ 0.25 kg/ha;

III Vl 0.25 +0.75, 0.75 0.25, 0.5 0.5 and 0.25

+ 0.25 kg/ha;

IV Vl 0.25 0.75, 0.75 +0.25, 0.5 0.5 and 0.25

+ 0.25 kg/ha.

After 12 to 16 days, it was ascertained that the mixtures I V, II V, III V, IV V, I VI, II VI, II] VI and IV VI had a better herbicidal action than that of their individual components, combined with the same good crop plant compatibility. The results of this experiment are given below:

kg/ha 0. 25 0.5 0.75 1.0

Crop plant:

Zea mays 0 O 0 0 Unwanted plants:

Amaranthus retroflexus l0 I6 Cyperus rotundus l0 I5 30 85 Digitaria sanguinalis 0 3 5 5 Portulaca oleracea 15 33 65 Setaria faberii 0 4 8 l0 kg/ha 0.25 0.5 0.75 1.0

Crop plant:

Zea mays 0 0 0 O Unwanted plants:

Amaranthus retroflexus 12 20 38 45 Cyperus rotundus I5 20 32 45 Digitaria sanguinalis 0 5 6 7 Portulaca oleracea 16 35 52 68 Setaria faberii 0 5 7 10 III kg/ha 0.25 0.5 075 L0 Crop plant:

Zea mays O 0 0 0 Unwanted plants:

Amaranthus retroflexus 14 30 45 55 Cyperus rotundus I2 20 35 45 Digitaria sanguinalis O 5 7 8 Portulaca oleracea I9 39 55 70 Setaria faberii 0 5 8 l0 kg/ha 0.25 0.5 0.75 1.0

Crop plant:

Zea mays 0 0 O 0 Unwanted plants:

Amaranthus retroflexus 20 30 35 4O Cyperus rotundus 7 I5 25 6O Digitaria sanguinalis O 5 7 l0 -cntmued kg/ha 0.25 0.5 0.75 1.0

Portulaca oleracea 22 40 57 70 Setarla faberii 0 8 l0 V kg/ha 0.25 0.5 0.75 l .0

Crop plant: Zea mays 0 0 0 0 Unwanted plants: Amaranthus retroflexus l0 18 24 30 Cyperus rotundus 5 l0 I5 20 Digitaria sanguinalis l0 21 3O 48 Portulaca oleracea 27 35. Setaria faberli 7 15 23 30 VI kglha 0.25 0.5 0.75 1.0

Crop plants: Zea mays 0 0 0 0 Unwanted plants: Amaranthus retroflexus 15 24 38 50 Cyperus rotundus 5 l0 17 25 Digitaria sanguinalis 15 25 39 52 Portulaca oleracea I9 58 80 Setaria faberii l0 15 20 25 l V kg/ha 0.25 0.75 0.75 0.25 0.5 0.5 025 0.25

Crop plant: Zea mays 0 0 0 0 Unwanted plants: Amaranthus retroflexus 69 78 75 Cyperus rotundus 60 67 5 8 53 Digitaria sanguinalis 70 61 49 Portulaca oleracea 86 96 93 Setaria faberii 57 52 5O 43 ll V kg/ha 0.25 0.75 0.75 0.25 0.5 0.5 0.25 0.25

Crop plant: Zea mays 0 O 0 0 Unwanted plants: Amaranthus retrofleux 77 I 81 68 55 Cyperus rotundus 62 69 71 60 Digitaria sanguinalis 71 I 57 72 51 Portulaca oleracea 84: 94 92 70 Setaria faberii 54 49 50 45 [II V kg/ha 0.25 0.75 0.75 0.25 0.5 0.5 0.25 0.25

Crop plant: Zea mays 0 0 0 0 Unwanted plants:- Amaranthus retroflexus 70 95 82 62 Cyperus rotundus 64 68 56 Digitaria sanguinalis 75 56 70 45 Portulaca oleracea 87 97 95 74 Setaria faberii 54 57 60 48 IV V kglha 0.25 0.75 0.75 025 0.5 0.5 0.25 0.25

Crop plant: Zea mays 0 0 0 0 Unwanted plants: Amaranthus retroflexus 87 78 70 Cyperus rotundus 70 97 75 68 Digitaria sanguinalis 68 52 65 49 Portulaca oleracea 80 96 91 78 Setaria faberii 54 50 5 2 49 l Vl kg/ha 0.25 +0.75 0.75 0.25 0.5 0.5 0.25 0.25

Crop plant: Zea mays 0 O 0 0 Unwanted plants: Amaranthus retroflexus 95 80 65 Cyperus rotundus 65 75 67 55 Digitaria sanguinalis 75 65 70 50 Portulaca oleracea 100 I00 85 Setaria faberii 60 55 60 50 cocklebur (X anthium pensylvanicum) were treated at a growth height of 2v to 17 cm with the following amounts of the following'individual active ingredients and mixtures thereof: I I I 3-.isopropyl-2, l ,3-benzothiadiazinone-(4)-2 ,2-dioxide, sodium salt 0.5, 1.0, 1.5, 2,0, 2,5 and 3.0 kg/ha, v

3-isopropyl-2, 1 ,3-benzothiadiazinone-(4)-2,2-

dioxide,-dimethylamine salt 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0'kg/ha;

dioxide, diethanolamine salt 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0 kg/ha 1V 3-isopropyl-2, 1 ,3-benzothiadiazinone-( 4)-2,2-

dioxide,

0.5, 1.0, 1.5, 2.0, 2.5 and 3.0 kg/ha;

V 2'-ethy1amino-4-( 1-methyl-3-oxabutyl)-amino-6- c hloro- 1 ,3,5-triazine,

0.5,10, 1.5, 2.0, 2.5. and 3.0 kg/ha;f

V1 2-chloro-4-ethylamino-6-isopropylamino- 1 ,3,5-

triazine,

0.5, 1.0, 1.5, 2.0, 2.5 and 3.0 kg/ha;.

V11 2-(2-chloro-4-ethylamino-1,3,5-triazin-6- ylamino )-2-methy1propionitrile,

0.5, 1.0, 1.5, 2.0, 2.5 and 3.0 kg/ha;

V111 N-'( 4-chlorophenyl )-N -methoxy-N methylurea, 1.0, 1.5, 2.0 and 3.0 kg/ha; I

3-isopropyI-2,1 ,3-benzothiadiazinone-(4)-2,2-

11 V1 kg/ha 0.25 0.75 0.75 0.25 0.5 0.5 0.25 0.25

Crop plant: Zea mays 0 0 0 0 Unwanted plants: V Amaranthus retroflexus 90 96 84 68 Cyperus rotundus 75 85 70 65 Digitaria sanguinalis 71 68 f s2 Portulaca oleracea 100 100 100 Setaria faberii 59 51 56 52 111 V1 kg/ha 0.25 0.75 0.75 0.25 0.5 0.5 0.25 0.25

Crop plant:

Zea mays 0 0 0 0 Unwanted plants: Amaranthus retroflexus 9 2 90 65 Cyperus rotundus 70 80 70 57 Digitaria sanguinalis 75 68 66 53 Portulaca oleracea 100 100 90 Setaria faherii 60 s9 65 60 I [V v1 kg/ha 0.25 0.75 0.75 +0.25 0.5 0.5 0.25 0.25

Crop plant: Zea mays 0 0 0 0 Unwanted plants: I 7 i Y v Amaranthus retroflexus 93 98 94 75 Cyperus rotundus 70 90 74 6O Digitaria sanguinalis 75. 68 70 55 Portulaca'oleracea 100 I i 100 100 90 Setaria faberii' 6 3 60 '65 55 0 no damage I i i 100 complete destruction EXAMPLE 3 0.5 and 1.5 1.5 kg/ha; Y I 1 11+ V 1.5 +0.5, 0.5 +1.5, 1.0 +1.0, 0.5 +2.5, 2.5 In the greenhouse the plants Indian corn (Zea mays), 0.5 and 1.5 1.5 kg/ha; redroot pigweed (Amarqnthus retroflexus). purple nut- 111+ V 1.5 0.5, 0.5 1.5, 1.0 1.0, 0.5 2.5, 2.5 sedge (Cyperus rotundus), large crabgrass (Digitaria 0.5 and 1 .5 1.5 kg/ha; sanguinalis), giant foxtail (Selariafaberii) and common 40 IV V 1.5 +0.5, 0.5 1.5, 1.0 1.0, 0.5 2.5, 2.5

0.5 and 1.5 1.5 kg/ha; ..1+V1 1.5 +0.5, 0.5 +1.5, 1.0 +1.0,'0.'5 2.5', 2.5

0.5 and 1.5 +1.5 kg/ha; 11+ V1 1.5 0.5, 0.5 +1.5, 1.0 +1.0,0.5 +2.5, 2.5 0.5 and 1.5 1.5 kg/ha; 111 +Vl 1.5+ 0.5, 0.5 +1.5, 1.0 +1.0, 0.5 +2.5, 2.5

+0.5 and 1.5 1.5 kg/ha', IV +V1l.5 +0.5, 0.5 +1.5,1.0 +1.0, 0.5 +2.5, 2.5

+0.5 and 1.5 1.5 kg/ha; 1+ V11 1.5 0.5, 0.5 +1.5, 1.0 +1.0, 0.5 2.5, 2.5

+0.5 and 1.5 1.5 kg/ha; 11+Vl1 1.5 +0.5, 0.5 1.5, 1.0+ 1.0, 0.5 +2.5, 2.5 0.5 and 1.5 1.5 kg/ha; 111+ V11 1.5 0.5, 0.5

+1.5,1.0+l.0, 0.5 +2.5, 2.5 +0.5 and 1.5 +1.5

k 1V+V111.5 +0.5, 0.5 +1.5, l.0+1.0, 0.5 +2.

+0.5and 1.5 1.5 kg/ha; 1+ V111 1.0 +1.0 and 1.5 +1.5kg/ha', 11.+ V111 1.0 1.0 and 1.5 1.5 kg/ha; 111+ V111 1.0 +1.0 and 1.5 +1.5 kg/ha; 1V +V111 1.0 +1.0 and 1.5 +1.5 kg/ha. After 12 to 14 days it was ascertained that mixtures of active ingredients 1 to V11 had superior crop plant compatibility combined with the good herbicidal action as their individual components. Mixtures with active ingredient V111 (non-inventive; used for comparison purposes) caused considerable damage to the crop plants.

The results of the experiment are given below:

l kg/ha 0.5 L 1.5 2.0 2.5 3.0

Crop plant: Zea mays 0 0 0 0 0 Unwanted plants: Amaranthus retroflexus 16 40 55 75 82 95 Cyperus rotundus 50 60 75 9O Digitaria sanguinalis 3 5 l0 l3 I5 20 Setaria faberii 4 l0 l5 19 2O 24 Xanthium pensylvanicum 20 50 60 78 86 95 ll kg/ha 0.5 L0 1.5 2.0 2.5 3.0

Crop plant Zea mays 0 0 0 0 0 5 Unwanted plants: Amaranthus retroflexus 20 60 80 90 98 Cyperus rotundus l8 45 60 80 95 100 Digitaria sanguinalis 5 7 l0 l4 17 20 Setaria faberii 5 8 l0 l4 19 23 Xanthium pensylvanicum 34 63 79 87 98 Ill kg/ha 0.5 1.0 1.5 2.0 2.5 3.0

Crop plant: Zea mays O 0 O 0 0 5 Unwanted plants: Amaranthus retroflexus 30 70 90 97 100 cyperus rotundus 20 45 65 90 95 I00 Digitaria sanguinalis 5 8 l0 l0 15 20 Setaria faberii 5 l0 l2 15 20 25 Xanthium pensylvanicum 36 75 84 95 100 W kg/ha 0.5 L0 1.5 2.0 2.5 3.0

Crop plants: Zea mays 0 0 0 0 0 5 Unwanted plants: Amaranthus retroflexus 30 40 60 80 95 100 Cyperus rotundus 25 80 90 95 100 Digitaria sanguinalis 5 l0 l0 l5 17 20 Setaria faberii 5 5 10 2O 22 25 Xanthium pensylvanicum 30 40 60 65 87 95 V kg/ha 0.5 1.0 1.5 2.0 2.5 3.0

Crop plant: Zea mays 0 0 0 0 5 l0 Unwanted plants: Amaranthus retroflexus 18 30 40 55 80 Cyperus rotundus 10 20 30 35 43 50 Digitaria sanguinalis 2| 48 65 90 95 I00 Setaria faberii 15 30 45 65 90 Xantium pensylvanicum 13 30 37 50 64 85 VI kg/ha 0.5 1.0 1.5 2.0 2.5 3.0

Crop plant: Zea mays 0 0 0 0 l0 l5 Unwanted plants: Amaranthus retroflexus 24 S0 68 95 98 I00 Cyperus rotundus I0 25 30 35 51 70 Digitaria sanguinalis 25 52 73 95 98 100 Setaria faberii 15 25 35 46 58 65 Xanthium pensylvanicum l() 22 30 43 50 69 VII kg/ha 0.5 1.0 L5 2.0 2.5 3.0

Crop plant: Zea mays 0 0 0 0 5 l0 Unwanted plants: Amaranthus retroflexus I5 Z7 4] 58 90 Cyperus rotundus l0 17 30 36 42 54 Digilaria sanguinalis 20 45 60 95 100 Setaria faberii I3 28 40 60 74 Xanthium pensylvanicum 10 20 34 45 52 H Vlll kg/ha 1.0 1.5 2.0 3.0

Crop plant: Zea mays 20 30 38 65 Unwanted plants: Amaranthus retroflexus 20 35 60 98 Cyperus rotundus 30 40 65 -contmued Vlll kg/ha 1.0 1.5 2.0 3.0

Digitaria sanguinalis 4O 65 85 100 Setaria faberii 36 50 70 100 Xanthium pensylvanicum 2O 32 45 90 l V kglha 1.5 0.5 0.5 1.5 L +1.0 0.5 2.5

Crop plant: Zea mays 0 0 O Unwanted plants: Amaranthus retroflexus 100 95 95 100 Cyperus rotundus 95 85 9O 90 Digitaria sanguinalis 97 92 lOO Setaria faberii 7O 90 90 100 Xanthium pensylvanicum 100 100 lOO 100 kg/ha 2.5 0.5 1.5 1.5 1.5 0.5 0.5 1.5

Crop plant: Zea mays O 0 0 O Unwanted plants: Amaranthus retmflexus lOO H10 100 95 Cyperus rotundus 100 I00 100 87 Digit-aria sanguinalis 80 100 95 Sctaria faherii 95 65 9O Xanthium pensylvanicum lOO lOO 100 100 100 ll V I kg/ha 1.0 +1.0 0.5 2.5 2.5 0.5 1.5 +1.5

Crop plant: 1 Zea mays 0 5 O O Unwanted plants: Amaranthus retroflexus l ()0 lOO 100 100 Cyperus rotundus 98 95 lOO 100 Digitaria sanguinalis 95 100 5 74 lOO Setaria faberii 78 lOO 75 95 Xanthium pensylvanicum 100 100 100 100 [II V kg/ha l.5 0.5 0.5 1.5 1.0 1.0 0.5 2.5

Crop plant: Zpa mays 0 0 O 5 Unwanted plants: Amaranthus retroflexus I00 97 100 100 Cyperus rotundus 100 88 97 97 Digitaria sanguinalis 70 98 95 100 Setaria faberii 68 90 100 Xanthium pensylvanicum 100 100 lOO 100 kg/ha 2.5 0.5 1.5 1.5 1.5 05 0.5 +1.5

Crop plant: Zea mays 0 0 0 0 Unwanted plants: Amaranthus retroflexus 100 100 100 100 Cyperus rotundus lOO 100 100 95 Digitaria sanguinalis 74 100 72 100 Setaria faberii 75 96 68 Xanthium pensylvanicum 100 100 100 IV V kg/ha l.0 L0 0.5 2.5 2.5 0.5 L5 1.5

Crop plant: Zea mays O 5 0 0 Unwanted plants: Amaranthus retroflexus l()() lOO lOO Cyperus rotundus I00 95 I00 100 Digitaria sangulnalis 97 lOO 8O lOO Setaria faberii 85 100 76 95 Xanthium pensylvanicum 100 100 100 K10 l Vl kg/ha 1.5 0.5 0.5 L5 1.0 +1.0 0.5 2.5

Crop plant: Zea mays 0 0 0 l0 Unwanted plants: Amaranthus retroflexus 100 100 100 lOO Cyperus rotundus 97 85 98 100 Digitaria sanguinalis 75 lOO 92 100 Setaria faberii 7O 8O 80 95 Xanthium pensylvanicum 100 90 100 97 -contmued l V] ll V] kg/ha 2.5 0.5 1.5 1.5 L5 0.5 0.5 +1.5

Crop plant: Zea mays O 0 (J Unwanted plants: Amaranthus retroflexus 100 l00 lOO lOO Cyperus rotundus 100 100 100 89 Digitaria sanguinalis 76 100 73 100 Setaria faberii 75 96 67 79 Xanthium pensylvanicum 100 l00 lol) 95 ll Vl kg/ha l.0 +1.0 0.5 2.5 2.5 1.5 l.5

Crop plant:

0 l0 0 O Zea mays Unwanted plants: Amaranthus retroflexus lOO lOO lOO lOO Cyperus rotundus 100 90 100 100 Digitaria sanguinalis 94 I00 80 100 Setaria faberii 69 96 74 87 Xanthium pensylvanicum 100 100 l00 100 Ill Vl kglha 1.5 0.5 0.5 1.5 L0 L0 0.5 2.5

Crop plant: Zea mays 0 0 0 l0 Unwanted plants: Amaranthus retroflexus l00 100 100 100 Cyperus rotundus 100 89 lOO 98 Digitaria sanguinalis 75 100 96 l00 Setaria faberii 67 82 7'3 95 Xanthium pensylvanicum l00 94 l()() 100 Ill Vl W Vl kg/ha 2.5 0.5 1.5 1.5 1.5 0.5 0.5 l.5

Crop plant: Zea mays 0 0 0 0 Unwanted plants: Amaranthus retroflexus I00 lOO I00 100 Cyperus rotundus I00 100 100 95 Digitaria sanguinalis 100 76 lOO Setaria faherii 73 96 68 80 Xanthium pensylvanicum 100 100 l00 96 W Vl kg/ha V 1.0 +1.0 0.5 2.5 2.5 0.5 L5 1.5

Crop plant: Zea mays 0 l0 0 0 Unwanted plants: Amaranthus retroflexus 100 lOO 100 100 Cyperus rotundus l()() 98 100 100 Digitaria sanguinalis 95 100 82 I00 Setaria faberii 70 96 80 87 Xanthium pensylvanicum 95 I00 100 100 l V]! kg/ha l.5 0.5 0.5 1.5 L0 1.0 0.5 +2.5

Crop plant: Zea mays 0 0 0 5 Unwanted plants: Amaranthus retroflexus 98 90 97 100 Cyperus rotundus 95 92 I00 Digitaria sanguinalis 70 95 100 Setaria faberii 67 80 75 l00 Xanthium pensylvanicum I00 97 98 l Vll ll Vll kg/ha 2.5 0.5 1.5 L5 1.5 0.5 0.5 1.5

Cro lant: Zea m ays 0 0 0 0 Unwanted plants: Amaranthus retroflexus 100 I00 98 95 Cyperus rmundus 100 100 95 98 Digitaria sanguinalis 85 98 70 95 Setaria faberii 70 V 95 63 85 Xanthium pensylvanicum 100 100 98 95 In the open the unwanted plants redroot pigweed (Amaranthus retroflexus), purple nutsedge (Cyperus rotundus), large crabgrass (Digitaria sanguinalis), giant foxtail (Setaria faberii) and common cocklebur (Xan- -contmued II VII kg/ha 1.0+ 1.0 0.5-+2.5. I 2.5 +0.5 I.5+l.5

Crop plant: I i i Zea mays 0 5 j I O 0 Unwanted plants: I Amaranthus retmflexus 100 100 I00 I00 Cyperus rotundus 96 92 100 100' Digitaria sanguinalis 90 100 87 98 Setaria I'aherii 74 I00 90 Xanthium pensylvanicum I00 100 I00 100 III+'VI1 kg/ha 1.5 0.5 05 1.5 1.0-l- 1.0 0.5 2.5

Crop plant: Zea mays 0 0 0 5 Unwanted plants: Amaranthus retroflexus I00 100 I00 I00 Cyperus rotundus 98 92 96 97 Digitaria sanguinalis 72 97 93 100 67 84 77 I00 Setaria I'aherii Xanthium pensylvanicum I00 100 100 100 111 VII IV Vll kg/ha 2.5 0.5 1.5 1.5 1.5 v+ 0.5 0.5 1.5

Crop plant: Zea mays O 0 0' 0 Unwanted plants: I I Amaranthus retroflexus I00 I00 100 100 Cyperus rotundus I00 I00 I00 98 Digitaria sanguinalis 77 98 70 95 Setaria faberii 76 97 64 82 Xanthium pensylvanicum 100 100 I00 100 IV VII kg/ha 1.0 +1.0 0.5 2.5" 2.5 0.5 1.5 +1.5

Crop plant: Zea mays 0 y 5 I 0 0 Unwanted plants: Amaranthus retroflexus 100 100 100 100 Cyperus rotundus 100 I00 100 100 Digitaria sanguinalis 97 v '100' 90 100 Setaria faberii I 100 77 94 Xanthium pensylvanicum 97 100 I00 100 .I VIII 1 11+ VIII kg/ha 1.0-1 1.0 l.5 +1.5 1.0-+1.0 1.5-+1.5

Crop plant: .Zea mays 21 33 I 25 39 Unwanted plants: I Amaranthus retroflexus 85 f 95 H 95 I00 Cyperus rotundus 80 96 '90 97 Digitaria sanguinalis I00 90 100 Setaria l'aberii 82 94 80 95 Xanthium pensylvanicum 95 95 100 111 VIII IV VIII kg/ha 1.0+1.0 1.5+1.5 1.0+1.0 I.5+I.5

Crop plant: Zea mays 24 35 30 49 Unwanted plants: Amaranthus retroflexus 96 I00 97 100 Cyperus rotundus 94 I00 95 I00 Digitaria sanguinalis 90 I00 96 100 Setaria faberii 80 I00 83 97 Xanthium pensylvanicum 96 I00 97 I00 0 no damage 100 complete destruction EXAMPLE 4 0.5. 1.0, 1.5 and 2.0 kg/ha;

II 2-ethyIamino-4-( I-methyl-3-oxabutyl )-amino-6- chloro-l ,3,5-triazine, 0.5, 1.0, 1.5 and 2.0 kg/ha',

III 2-ch1oro-4-ethyIamino-6-isopropylamino-1 ,3 ,5-

triazine, 0.5, 1.0, 1.5 and 2.0 kg/ha;

IV 2-chIoro-4,6-diethylamino- I ,3,5-triazine,

0.5, 1.0, 1.5 and 2.0 kg/ha;

1+ 11 1.5 0.5, 0.5 +1.5 and 1.0 +1.0 kg/ha;

1 +111 1.5 0.5, 0.5 +1.5 and 1.0 +1.0 kg/ha;

1+ IV 1.5 +0.5, 0.5 +1.5 and 1.0 +1.0 kg/ha.

After 2 to 3 weeks it was ascertained that the mixcominued tures I ll, 1 111 and I [V had a better herbicidal ac- II tion than their individual components, combined with kg/ha 15 the same 00d CI'O lant com atibilit Amaranthus retroflexus 90 97 100 p Cyperus rotundus 90 89 96 The results of th1s experiment are given below: 5 Dlgiwiu sanguinulis 97 75 87 Setaria faberii 68 65 75 I Xanthium pensylvanicum 80 80 81 g/ a 0.5 1.0 1.5 2.0 1+ 111 kg/ha 0.5+ 1.5 1i5+o.5 1.0+ 1.0 Crop plant: Zea mays 0 0 O 0 1O Crop plant: Unwanted plants: Zea mays 0 O O Amaranthus retroflexus 28 35 55 75 Unwaflled P Cyperus rotundus 22 6Q 70 80 Amaranthus retroflexus 100 98 100 Digitaria sanguinalis 4 8 10 14 C{R YOWHQUS 95 97 99 Seariu faberii 3 5 9 l5 sDgltill'litt sangumahs 9g 8] 96 i etaria aberii 7 60 67 Xanthium pensylvanlcum 24 35 54 60 15 Xanthium pensylvanicum 89 85 93 11 1+ 1v kglha L0 5 kg/ha 0.5 1.5 1.5 0.5 1.0 1.0

Crop plant: Crop plant: Zea mays O 0 0 0 Zea mays 0 0 0 Unwanted plants: 2 Unwanted plants: Amaranthus ret fl 15 2 35 54 0 Amaranthus retroflexus 95 90 98 Cyperus m d 9 3 23 35 Cyperus rotundus 84 97 92 Digitaria sanguinalis 45 e3 80 i l 2g 23 2g Setaria faberii 10 24 35 49 f l l 1 75 8O 78 Xanthium pensylvanicum 10 20 28 40 an pensy vdmcum O no damage k lh 0 5 1 0 Ill 1 5 5 I00 complete destruction Crop plants: I claim: fl y l 0 0 0 0 l. A herbicide composition containing a herbicidally mig i g exus 2O 47 63 85 effective amount of a mixture consisting essentially of Cyperus rotundus 9 23 23 33 a. a member selected from the group consisting of 2- sDlgitaria sijanguinalis 24 50 72 90 ethylam1n0-4-( l-methyl-3-oxabutyl )ammo-6- j z gz i5 1; chloro-l,3,5-triazine, 2-chlor0-4-ethylamino-6-is0- propylamino-l,3,5-triazine, and 2-(2-chloro-4- k h IV 2 ethylaminol ,3,5-triazin-6-ylamin0)-2-methylpro- 35 pionitrile, and Crop plan: b. a member selected from the group consisting of 3- Zea mays 0 0 0 0 isopropyl-2, l ,3-benzothiadiazinone-(4)-2,2-di0xnexus 17 30 43 57 ide or the sod1um, dimethylamine, or diethanolcyperus rotundus 7 13 I8 25 amme salt thereof in a weight ratio of compounds Digitaria san g uinalis 15 31 4g 6 ab 1n the range'of l:Q.2-5, respectively. sitar}? fabern l 11 a? 7 3 40 2. A herbicide composition contammg a herbicidally Pemy 20 effective amount of a mixture consisting essentially of 1 +1 'a. 2-chloro-4,6-diethylamino-l ,3,5-triazine, and kg/ha 05 140 W b. 3-isopropyl-2,l ,3-benzothiadiazinone-(4)-2,2-

dioxide in a weight ratio of (a) to (b) in the range Crop plant: 4 f t 13 Zea mays 0 O 0 5 O O Unwanted plants: 

1. A HERBICIDE COMPOSITION CONTAINING A HERBICIDALLY EFFECTIVE AMOUNT OF A MIXTURE CONSISTING ESSENTIALLY OF A. A MEMBER SELECTED FROM THE GROUP CONSISTING OF 2ETHYLAMINO-4-(1-METHYL-3-OXABUTYL)AMINO-6-CHLORO1,3,5-TRIAZINE, 2-CHLORO-4-ETHYLAMINO-6-ISOPROPYLAMINO1,3,5-TRIAZINE, AND 2-(2-CHLORO-4-ETHYLAMINO-1,3,5-TRIAZIN-6-YLAMINO)-2-METHYLPROPIONITRILE, AND B. A MEMBER SELECTED FROM THE GROUP CONSISTING OF 3-SIOPROPYL-2,1,3-BENZOTHIADIAZINONE-(4)-2,2-DIOXIDE OR THE SODIUM, DIMETHYLAMINE, OR DIETHANOLAMINE SALT THEREOF IN A WEIGHT RATIO OF COMPOUNDS A:B IN THE RANGE OF 1:0,2-5, RESPECTIVELY.
 2. A herbicide composition containing a herbicidally effective amount of a mixture consisting essentially of a. 2-chloro-4,6-diethylamino-1,3,5-triazine, and b. 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide in a weight ratio of (a) to (b) in the range of 3:1 to 1:3. 